Aromatic ammonium compounds and process of making same.



r earns a Fro STALAY ARTHUR HOLT, OF LUDWIGSHAFEN-ON--THE-RHI1 TE, AND OTTO SCHMIDT. OF MANNHEIM, GERMANY. ASSIGNORS TO BADISCHE ANILIN & SODA FABRIK, OF LUDWIGSHAFEN-ON-THE-RHINE. GERMANY, A CORPORATION.

- AROMATIC AMMON IUM COIVIPOUNDS AND PROCESS OF llIAKING SAME.

No Drawing.

Specification of Letters Patent.

To U whom it may ('oi'zccl'n:

Be it known that we. l'lX-IZJRY Sramr -uz'rili'n llUL'l' and ()T'ro Scnunrr, subjects, respectively, otthe King of England and the King of Prussia, residing, respectively, at Llulwigshaten-onthe-lthine and Mannheim, Germany, doctors of philosophy and chemists, have invented new and useful lmprorements in Aromatic Ammonium Compounds and Processes of Making Same, of which the following is a specification.

Our invention relates to the manufacture and production of new aromatic ammonium compounds which contain at least one aralkyl residue, which residue contains at least one acid group ca pable of forming a salt. Under the expression acid group capubic of forming a salt we include a sult'ouic acid group and a carboxylic acid group, either in the tree torm'or otherwi e.

()ur new compounds can be obtained, "for instan e, by reacting on a tertiary amino compound with a halogen aralkyl compound which contains the halogen in the side chain and which also contains a group capable of forming a salt, such for instance as a sult'onic acid group and a carboxylic acid group lt, instead of the tree sulfonic acid orthe tree carboxylic acid, the esters thereof be emploved, the corresponding derivatives of the aforesaid arallty-l ammonium sultonic acids, or aralkyl ammonium carboxylic acids, can be obtained. The ammonium compounds containing a snlfonatcd arallcyl residue can also be produced by tr rating the corresponding a-mi'nonium compound with a sult'onating agent, such for instance as concent 'a-ted sulfuric acid. According to the energy with which the. sulionating agent is allowed to react. either one, or more than one, sulfonic acid group can be introduced into the said ammonium compound. but at least one sultonic acid group .mustalways be introduced into the a 'allryl residue. If desired, a monosultonic acid of an aralltyl an'm'ionium compound which has been prepared, for instance. by combining an aralkyl haloid with a tertiary amin monosulfonic acid containing the sult'onic acid group 11 an aryl residue. can be treated with a suitable sullionatine agent and in this manner a sullionic acid grou ii'itroduced into the aralltyl residue. As instances ofthe new compounds which can beproduced according to our invention we mention the products obtainable by treating benzylchlorid-sultonic -acid with dimethyl-anilin, or by treating benzyl-chloridpara-carboxylic acid with dimethyl-anilin, or by acting with a sult'onating agent. on the compounds produced by condensing a trialkyl-amin or a dialkyl-arylamin with benzyl chlorid, or a homologue or an analogue thereof, or with a substitution productof any of these compounds, and as particuiar instances we mention dimethyl-phenylbenzyl-ammonium chlorid (Bdfiicht, 10, p. 2079), trimethyl-benzyl-ammonium chlorid '(Joumal 0f the Chemical Society, 57, p. 778), and also naphthalene-trimethylphenyl-amnionium chlorid (obtainable by condensing together omega-chlor-hetamethyl-naphthalenc and, dimethyl-anilin) and further the compounds obtainable by reacting with benzyl ehlorid on tetra-methyldiamino-diphcnyl-methane or on leuco-malachite green.

Our new compounds are characterized by being colorless and crystallizable bodies, which GOIll'tllll nitrogen and an aralkyl residue to which at least one acid group capable of forming a salt is attached, and further they react with indigo white to form yellow compounds which are soluble in dilute alkali. From their chemical. behavior the sult'onic acids appeargenerally to be inner anhydrids between a sultonic acid group and the hydroxyl group of the ammonium compounds, and we wish to be understood as claiming our new compounds whether the acid group capable of forming a salt bcin the free form, or whether it be masked in any way, for instance, by the for mation of an inner anhydrid as aforesaid. Our new compounds can be conveniently brought on the market in the form of their salts, or esters, or anhydrids, for instance the disulitonic acid of din1ethyl-phenylbenzybammonium chlorid can be employed in the. form in which one of thetsulfonic acid groups neutralized with calcium, while the other takes part in the formation of an innor anhydrid.

The following examples will serve to illusstrate further the nature of our invention and how it can be carried into practical e'llect, but the invention is not confined to these examples. The parts are by weight.

Patented Aug". 20, 1912.

Application filed September 27, 1910. Serial No. 584,131.

low it to cool and remove the dimethyl-ani lin hydrochlorid, as well. as any excess of dimethyl-anilin, by means of warm alcohol. The residue consists of a white powder which is easily soluble in water, but is in soluble in ether and alcohol, and according to analysis appears to possess a constitution corresponding to the formula:

' cng.a cns acan Example 2: Heat together,.for from seven to eight hours, at from sixty to seventy degrees Centigrade, thirty-four parts of dimethyl-anilin, and seventeen parts of benzyl chlorid carboxylic acid, obtainable from para-toluic acid chlorid by chlorinating, while hot, in the absence of chlorin carriers, and then saponifying the benzyl chlorid carboxylic acid chlorid with ninety-six per cent. sulfuric acid at zero centigrade. When the mixture is cold, break it up into small pieces and extract, by means of ether, any excess of. dimethyl-anilin. The product is easily soluble in water and in alcohol, but is insoluble in ether. It can be recrystallized from a mixture of ether and alcohol and thus be obtained in the form of needles which melt at one hundred and fifty-one degrees centigrade under decomposition. Instead of dimethyl-anilin, other tertiary amine can be employed.

Example 3: Introduce two hundred and fifty parts of dimethyl-phenyl-benzyl-am monium chlorid, without cooling, into seventy parts of ninety-seven per cent. sulfuric acid, allowing the hydrochloric acid which is evolved to escape, and then pass a current of dry air through the solution, in order to remove the remainder of the hydrochloric acid. Add gradually, seven hundred parts of fuming sulfuric acid containing twentythree per cent. of free 80,, maintaining the temperature between twenty-five and thirty degrees centigrade; then heat, the mixture for a short time, on the water-bath, cool, and pour on to ice and remove the sulfuric acid by means of lime. Evaporate the filtrate to a small volume, whereupon the anhydrid of dimethyl-phenyl-benzyl-ammonium-hydroxy-sulfonic acid separates out in large colorless crystals. It melts at a high temperature, is insoluble in alcohol, but is fairly easily soluble in water. In a similar manner, other aromatic ammonium bases, or their salts, can be sulfonated, such tor instance as the compound obtainable from benzyl chlorid and tetra-methyl-diamino-diphenylemethane, or the compound obtainable from benzyl chlorid andleuco malachite green.

Example 4: If, in the foregoing Example 3, instead of seven hundred parts of fuming sulfuric. acid containing twenty-three per cent; of free SO, four hundred and twenty-five parts of acid containing sevent per cent. of free SO, be employed, the disulfonic acid of dimethyl-phenyl-bcnzylammonium hydroxid can be obtained. Probably anhydrid formation takes place between one sulfonic acid group and the ammonium hydroxi'dgroup. This acid and its salts are very easily soluble in water and can be obtained from their solution by evaporation.

Example 5: Introduce two hundred and ninety-one parts of dimethyl-phenyl-benzylammonium sulfonicacid anhydrid (obtainable from dimethybanilhi-meta sulfonic acid and bcnzyl chlorid) into seven hundred parts of fuming sulfuric acid containing twenty-three per cent. 'of free, S0,, and heat for some time at from one hundred to one hundred and ten degrees centigrade. After cooling, pour the mixture into water, neutralize with lime and evaporate the filtrate to dryness, whereupon a calcium salt of dimcthyl-phenyl-benzyl-ammonium hydroxid disulfonic acid is obtained. This acid is probably isomeric with that obtainable according to the foregoing Example 4.

Now what we claim is 1. As new compositions of matter aromatic quaternary ammonium compounds containing at least one aralkyl residue,

which residue contains at least one acid group capable of forming a salt, which new compounds are colorless and crystallizalole bodies, containing nitrogen, and which react with indigo white to form yellow compounds which are soluble in dilute alkali.

2. As new compositions of matter aro-- matic quaternary ammonium compounds containing atv least one aralkyl residue, which residue contains at least one sulfonic acid group, which new compounds are colorless and crystallizable bodies, containing nitrogen, and which react with indigo white to form yellow compounds which are soluble in dilute alkali.

' 3. As a new com osition of matter, dimethyl-phcnyl-benzy- :ammoniumhydroxidsulfonic-acid anhydrid which is colorless andieasily solublein water, which contains nitrogen and sulfur, and which reacts with indigo white to form a yellow compound which ,is soluble in dilute alkali.

4. The process of producing aromatic quaternary ammonium compounds containing at least one aralkyl residue, which resi- 'dne contains at least one sulfonic acid group, by reacting with a sulfonating agent furic acid containing seventy per cent. of on a quaternary ammonium compound free SC) substantially as herelnbefore dewhich contains at least one aralkyl residue. scribed. 15

5. The process of producing a sulfonic In testimony whereoi' we have hereunto 5 acid derivative of dimethyl-phenyl-benzylset our hands in the presence of two subaminonium hydroxid by treating dimethylscribing Witnesses. phenyl-benzyl-ammonium chlorid with a sulfonatino agent I I HENRY STALAY ARTHUR HOLT.

6. The iorocess of producing dimethyl OTTO SCHMIDT 10 phenyl-benzylammonium hydroxid-disu1- Vitn'sses: fonic-acid-anhydrid by nacting on dimethyl- J. ALEC. LLOYD,

pheny1-benzy1-ammonium chlorid with S111-: JosEF PFEIFFER. 

